Coumarin dyes and side-chain coumarin dye-substituted polymers which exhibit nonlinear optical properties

Abstract

Coumarin dyes such as alkylaminocoumarincarboxamides which have functional hydroxyl groups or which are chemically attached to vinyl monomers such as methacrylic acid. The dyes which are chemically attached to vinyl monomers can be copolymerized, e.g. with acrylic monomers to produce a coumarin dye-containing polymer. The dyes which have functional hydroxyl groups can be reacted with an existing polymer or copolymer, e.g. a copolymer of styrene and acrylic acid to esterify the acid groups of the polymer to form a coumarin dye-containing polymer. Such coumarin dye-containing polymers are formed into films and fibers which when poled in an electric field yield a film or fiber with nonlinear optical properties.

What is claimed is: 
     
       1. Coumarin dye-containing polymers which are water insoluble, having second-order nonlinear optical properties, which are characterized by a recurring monomeric unit corresponding to the formula: ##STR10## where P is a polymer main chain unit; and, where D is a coumarin dye selected from the group consisting of: ##STR11## where R and R 2  are independently selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, and alkenyl of 1 to 22 carbon atoms; where G is selected from the group consisting of H, --CH 3 , and --CF 3  ;   where A and B are independently selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, and the atoms necessary to complete a 6-membered ring; and, where n=2 to 18.   
     
     
       2. Coumarin dye-containing polymers as defined in claim 1, where P is selected from the group consisting of a styrenic unit and an acrylic funit. 
     
     
       3. Coumarin dye-containing polymers as defined in claim 1, where P is an acrylic unit. 
     
     
       4. Coumarin dye-containing polymers as defined in claim 1, where P is a styrenic unit. 
     
     
       5. Coumarin dye-containing polymers as defined in claim 1, where P is selected from the group consisting of: ##STR12## where R 1  is selected from the group consisting of H or alkyl of 1 to 22 carbon atoms; where R 7  is selected from the group consisting of H and --COOR 1  ; and,   where F is --O--, --NH--, or --CH 2  --O--.   
     
     
       6. Coumarin dye-containing polymers as defined in claim 1, where D is selected from the group consisting of: ##STR13## where R and R 2  are independently selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, and alkenyl of 1 to 22 carbon atoms; where G is selected from the group consisting of H, --CH 3 , and --CF 3  ;   where A and B are independently selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, alkenyl of 1 to 22 carbon atoms, and the atoms necesary to complete a 6-membered ring; and,   where n=2 to 18.   
     
     
       7. Coumarin dye-containing polymers as defined in claim 1, further comprising non-coumarin containing main chain units, which can be illustrated by the formula: ##STR14## where R 3 , R 4 , R 5 , and R 6  are independently selected from the group consisting of alkyl, alkenyl, aryl, substituted aryl, cyano, amide, halogen, alkoxy, or --COOR 8 , where R 8  is is selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, and alkenyl of 1 to 22 carbon atoms; and, where y is at least 3, (x+y+z) ranges from 3 to about 3000, and y/(x+y+z) is 0.10 to 1.0.   
     
     
       8. Coumarin dye-containing polymers as defined in claim 7, where P is selected from the group consisting of a styrenic functional unit and an acrylate functional unit. 
     
     
       9. Coumarin dye-containing polymers as defined in claim 7, where n=2 to 6. 
     
     
       10. Coumarin dye-containing polymers as defined in claim 7, where D is selected from the group consisting of: ##STR15## where R and R 2  are independently selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, and alkenyl of 1 to 22 carbon atoms: where A and B are independently selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, alkenyl of 1 to 22 carbon atoms, and the atoms necessary to complete a 6-membered ring;   where G is selected from the group consisting of H, --CH 3 , and --CF 3  ; and, where n=2 to 18.   
     
     
       11. Coumarin dye-containing polymers as defined in claim 10 wherein R is H; R 1  and R 3  are methyl; R 4  is --COOCH 3  ; and, z=0. 
     
     
       12. Coumarin dye-containing polymers as defined in claim 10, where R is H, R 1  and R 3  are CH 3 , R 4  is aryl, and z=0. 
     
     
       13. Coumarin dye-containing polymers as defined in claim 12, where n=2. 
     
     
       14. Coumarin dye-containing polymers as defined in claim 10, where R 3  is H, R 4  is t-butyl phenyl, D is ##STR16## where both A and B are ethyl; G is H; n=2-6; and, z=0. 
     
     
       15. Coumarin dye-containing polymers as defined in claim 11, where n=2. 
     
     
       16. Coumarin dye-containing polymers as defined in claim 11, where n=5. 
     
     
       17. Coumarin dye-containing polymers as defined in claim 11, where both A and B are the atoms necessary to complete a 6-membered heterocyclic ring. 
     
     
       18. Coumarin dye-containing polymers as defined in claim 7, where D is ##STR17## where R is selected from the group consisting of H, and alkyl of 1 to 22 carbon atoms; where G is selected from the group consisting of H, --CH 3 , and --CF 3  : where n=2 to 18; and   where both A and B are selected from the group consisting of H, alkyl of 1 to 22 carbon atoms, alkenyl of 1 to 22 carbon atoms, and the atoms necessary to complete a 6-membered heterocyclic ring.   
     
     
       19. Coumarin dye-containing polymers as defined in claim 18 wherein both A and B are the atoms necessary to complete a 6-membered heterocyclic ring. 
     
     
       20. Coumarin dye-containing polymers as defined in claim 19, where n=2-6. 
     
     
       21. Coumarin dye-containing polymers as defined in claim 18 wherein both A and B are ethyl. 
     
     
       22. Coumarin dye-containing polymers as defined in claim 21, where n=2-6. 
     
     
       23. Coumarin dye-containing polymers as defined in claim 21, where n=2. 
     
     
       24. An optically nonlinear polymer film comprising the coumarin dye-containing polymer of claim 1. 
     
     
       25. An optically nonlinear polymer film comprising the coumarin dye-containing polymer of claim 11. 
     
     
       26. An optically nonlinear polymer film comprising the coumarin dye-containing polymer of claim 23. 
     
     
       27. A device comprising a film in accordance with claim 24.